US3927126A - Process for the manufacture of polyfluoroalcohols and their use - Google Patents

Process for the manufacture of polyfluoroalcohols and their use Download PDF

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Publication number
US3927126A
US3927126A US333246A US33324673A US3927126A US 3927126 A US3927126 A US 3927126A US 333246 A US333246 A US 333246A US 33324673 A US33324673 A US 33324673A US 3927126 A US3927126 A US 3927126A
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formula
polyfluoroalcohols
water
phosphorus
compounds
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US333246A
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Helmut Huber-Emden
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/40—Halogenated alcohols perhalogenated

Definitions

  • polyfluoroalcohols correspond to the formula wherein R, is a perfluorinated hydrocarbon radical with 1 to 22 carbon atoms, and R hydrogen, methyl, or hydroxymethyl. They are obtained from phosphorus-containing polyfluoro-compounds of the formula R,- l-I-O-POCl,
  • R is hydrogen, methyl or -CI-I OPOC1 by hydrolysis with water or water donating compounds.
  • the polyfluoroalcohols are useful as oilrepellants for various substrates or as intermediates for the manufacture of oil-repellants.
  • the present invention relates to a process for the manufacture of polyfluoroalcohols of the formula wherein R, represents a perfluorinated hydrocarbon radical with 1 to 22, preferably 1 to 16, carbon atoms, and R represents a hydrogen atom, a methyl group or a hydroxymethyl group, wherein phosphorus-containing polyfluoro compounds of the formula in which R, has meaning given hereinabove and R represents hydrogen, methyl or the radical of the formula -CH, 1 0C1 are hydrolysed with water or water donating compounds.
  • the perfluorinated hydrocarbon radical can be, for example, a straight-chain or a branched perfluoroalkyl radical with 4 to 17 carbon atoms and corresponds more or less to the following formulae:
  • polyfluoroalcohols of the formula wherein R has the indicated meaning and n is an integer from 6 to 12, and also those of the formula CI- H wherein n is the integer 6, 8, 10 or 12.
  • polyfluoroalcohols are also those of the formulae
  • the polyfluoroalcohols are obtained preferably by hydrolysis of phosphorus containing perfluoro compounds of the formula wherein R represents a hydrogen atom, a methyl group or the radical of the formula c1-1 0 P00, and n is an integer from 4 to 14.
  • n is the integer 6, 8, 10 or 12
  • the appropriate procedure for manufacturing the polyfluoroalcohols is to suspend the phosphorus-containing polyfluoro compound in water with stirring, and then to carry out the hydrolysis at the boiling temperature of the water. During the course of the reaction, the suspended reaction mixture forms initially a viscous solution; and towards the end of the reaction a fluid one.
  • the reaction velocity of the hydrolysis of the phosphorus-containing polyfluoro starting compounds depends very greatly on the temperature. In boiling water and under normal pressure, the hydrolysis lasts about hours or more in order to obtain a good yield of 3 polyfluoroalcohols. However, the reaction time can be substantially reduced by the application of higher temperatures in pressure vessels. The temperature range is between about 100 and 180C.
  • Another suitable method is to use as hydrolysis medium high boiling compounds which split off water under strongly acid conditions. Examples of such high boiling compounds are ethylene glycol, dihydroxypropane-l ,2, or glycerol.
  • the reaction product is precipitated from the reaction medium as an oily phase or in the form of a waxlike substance.
  • the water or glycol is decanted off and the reaction product is washed with hot water until it shows neutral reaction. It is also possible to pre-purify it by steam distillation. In this state, the reaction products still contain slight amounts of water and other impurities. They can be obtained in pure form by means of vacuum distillation or sublimation.
  • polyfluoroalcohols are valuable intermediates for the manufacture of oil repellants. But they can also be used themselves as oil repellants and are used, for example, for giving oleophobic finishes to porous and nonporous substrates by either incorporating them into the particular material or applying them to its surface.
  • porous substrates are meant, for example, leather and paper, but preferably textile fibres; wheras suitable non-porous materials, besides glass, are especially metals and plastics.
  • Textile fibre materials claim particular interest for the finishing with the polyfluoroalcohols.
  • Such materials include, for example, those made from natural or regenerated cellulose, such as cotton, linen or rayon, staple fibre or cellulose acetate; also from wool, synthetic polyamides, polyesters or acrylonitrile and the corresponding fibre blends.
  • the textiles can be in the form of threads, fibres and flocks, but preferably of woven or knitted fabrics.
  • the polyfluoroalcohols are applied from oranic solvent liquors by means of known processes, e.g., by the pad or immersion process.
  • Suitable solvents for the application are, for example, solvents which are immiscible, or only sparingly miscible, with water, such as benzene and benzenes which are halogenated or substituted with low molecular alkyl groups, e.g., toluene, xylene, ethylbenzene, cumene, monoand dichlorobenzene, but preferably halogenated hydrocarbons, e.g., the solvents trichloroethylene and perchloroethylene used in the dry cleaning industry, also chloroform, methylene chloride, carbon tetrachloride, dibromoethylene and the chlorinated ethanes, such as 1,1-dichloroethane, 1,2-dichloroethane, 1,1,l-trichloroethane and l,l,2,2,-tetrachloroethane.
  • solvents which are immiscible, or only sparingly miscible, with
  • the water-miscible solvents form another group including, e.g., ketones. such as acetone, methyl ethyl ketone, cyclohexanone, ethers and acetals, such as diisopropyl ether, diphenylene oxide, dioxan, tetrahydrofuran; also pyridine, acetonitn'le, ethylene carbonate, 'y-butyrolactone, N,M-dimethyl formamide, N,N- dimethyl acetamide, N-methylpyrrolidone, tetramethyl urea, tetramethylene sulphone. Mixtures of the cited solvents can also be used.
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethers and acetals, such as diisopropyl ether, diphenylene oxide, dioxan, tetrahydrofuran
  • pyridine
  • Preparations which contain the polyfluoroalcohols can also contain further suitable additives, e.g., tertiary amines, which are able to improve the reaction between the finishing agent and the substrate.
  • suitable additives are aliphatic and aromatic amines, for example trimethylamine, triethylamine or pyridine, which are applied in an amount of l to 5 moles, preferably 1 4 mole to 3 moles, relative to the amount of reaction product to be applied.
  • the temperature range for the application is generally between 20 and C, preferably between 40 and 80C.
  • the treatment times are generally between 1 and 30 minutes, preferably between 5 and 15 minutes.
  • the amounts in which the polyfluoroalcohols are applied can vary within wide limits and, in the padding process, amounts to, e.g., 0.1 to 10%, relative to the impregnating liquor, or, e.g., 0.1 to 10%, preferably 0.5 to 5%, relative to the fibre material, if the immersion process is followed.
  • the substrates treated in this way display a good oil repellency. It is also possible to produce a soil release and antisoiling effect with the polyfluoroalcohols.
  • the oil repellent can be applied in one operation either alone or together with the application of further finishing agents, in so far as these can be applied from organic solvents.
  • EXAMPLE 1 3.75 g of phosphoric acid (1-n-perfluoro-octyl-2- chloro)ethyl ester dichloride in 40 ml of water are refluxed for 160 hours in a 500 liter flask. The bath temperature is C. At the onset of the reaction vigorous foaming occurs. Within about 1 to 2.hours a clear reaction solution is obtained which is initially viscous, but becomes fluid towards the end of the reaction. The reaction product is precipitated during the reaction in the reflux cooler in the form of a gelatin-like substance. It is periodically removed from the cooler and collected.
  • reaction product is stirred in 50 ml of hot (90C) water, in the process of which it melts and is precipitated as a heavy oily phase, which congeals on cooling.
  • the water is decanted off and the reaction product is dried between filter paper.
  • the product is further purified by distillation in a saber flask (b.p. 104C/ 16 Torr) or by sublimation at a temperature of about 50 to 55C/0.001 Torr, to give the compound of the formula (4.2.).
  • EXAMPLE 2 a 3.75 g of phosphoric acid-( l-n-perfluoro-octyl-2- chloro)ethyl ester dichloride are dissolved with heating in 20 ml of water and the solution is shaken in a Carius tube for 25 hours at C. Upon cooling, the water is decanted off from the congealed reaction product. The product is stirred with hot water until it shows neutral reaction, in the process of which it melts and then congeals again on cooling. It is dried with filter paper to give 3.45 g of crude product which melts at 6263C.
  • the homologous alcohol of the formula (5.2) is manufactured from phosphoric acid-( l-n-perfluoro-octyl-Z-chloro )-propyl ester dichloride.
  • the reaction product is purified by sublimation a 57C/0.00l Torr.
  • EXAMPLE 4 a 6.17 of a homologue mixture of the formula (101 F(CF,), CHOPCI2 CH Cl with the composition r 6 8 I0 12 mol 23.5 43.6 25.4 1.3
  • the two phase reaction mixture is allowed to settle well and the upper phase is removed.
  • the lowerphase is treated with 300 ml of water and stirred for 3 hours at C.
  • the upper aqueous phase is removed and the lower, solid phase is distilled in a saber flask, to yield 313.6 g (94.2% of theory) of the perfluoroalkylchlorohydrin homologue mixture of the formula (104) F(CF ),CH--OH ca e] which boils in the range 76-l38C/ l 7 Torr.
  • the composition determined by gas chromatography is:
  • EXAMPLE 5 a While stirring thoroughly, 24.6 g of phosphoric acid-( l-n-perfluoro-octyl-2-chloro)-ethyl ester dichloride together 80 ml of ethylene glycol are heated for 7 hours to C (bath temperature) using a reflux cooler. The reaction mixture remains two phase to the end.
  • the lower phase is isolated and washed 6 times with 40 ml of hot water on each occasion (until its melting point is 6l63C after cooling).
  • the resulting compound corresponds to the formula EXAMPLE 6
  • 6.62 g of a bifunctional phosphoric acid monoester dichloride of the formula (12) are dissolved with heating in 60 ml of water and the solution is subsequently shaken in a Carius tube for 50 hours at 140C.
  • reaction product is precipitated as a wax-like substance. It is isolated and purified by steam distillation. The distillation is extracted with ether and the ether phase is dried over sodium sulphate. The solvent is removed to yield a wax-like product which is further purified by sublimation at 65C/0.01 Torr. A reaction product of the formula (6.1) is obtained.
  • R has the meaning given hereinabove and R represents hydrogen, methyl or the radical of the formula cH 0 POCI are hydrolysed in a high boiling water donating compound selected from the group consisting of ethylene glycol, dihydroxy propane- 1,2 and glycerol at temperatures of 100 to 180C. 1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Surface Treatment Of Glass (AREA)
  • Coloring (AREA)
US333246A 1972-02-22 1973-02-16 Process for the manufacture of polyfluoroalcohols and their use Expired - Lifetime US3927126A (en)

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CH255272A CH565724A5 (en)) 1972-02-22 1972-02-22

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JP (1) JPS4896505A (en))
BE (1) BE795705A (en))
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DE (1) DE2307204A1 (en))
FR (1) FR2173033B1 (en))
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SU (1) SU460615A3 (en))

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002369A1 (de) 1979-01-24 1980-08-07 Minnesota Mining & Mfg Verfahren zur schmutz- und fleckenabweisenden ausruestung von textilen bodenbelaegen oder des textilen ausgangsmaterials und fluessiges mittel zur durchfuehrung des verfahrens
US4382891A (en) * 1980-05-09 1983-05-10 E. I. Du Pont De Nemours And Company Use of fluoroalkoxysulfur fluorides in fluorinations
US4517376A (en) * 1981-06-26 1985-05-14 E. I. Du Pont De Nemours And Company Manufacture of chloromethyl-substituted polyfluoroalkyl esters
US5242487A (en) * 1988-11-11 1993-09-07 Daikin Industries Ltd. Water- and oil-repellant composition
DE3051167C3 (de) * 1979-01-24 1994-11-24 Minnesota Mining & Mfg Fluorierte Alkohole
US20080113200A1 (en) * 2006-11-13 2008-05-15 Sheng Peng Fluoroalkyl phosphate compositions
US20080113085A1 (en) * 2006-11-13 2008-05-15 Sheng Peng Polyfluoroether-based phosphates
CN110184847A (zh) * 2019-05-17 2019-08-30 华南理工大学 一种撕不烂仿皮纸及其制造方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2725394A (en) * 1950-08-03 1955-11-29 Ici Ltd Production of esters of orthophosphoric acid and salts thereof
US2866807A (en) * 1954-04-15 1958-12-30 Virginia Carolina Chem Corp Aliphatic aryl phosphites
US2929833A (en) * 1958-04-23 1960-03-22 Ethyl Corp Process of preparing phenyl dimethyl phosphates
US2960527A (en) * 1958-08-20 1960-11-15 Akad Wissenschaften Ddr Process for the preparation of dichloro phosphoric esters
US3059016A (en) * 1959-08-05 1962-10-16 Celanese Corp Manufacture of aryl phosphate esters
US3254142A (en) * 1961-09-01 1966-05-31 Bayer Ag Phosphorous acid esters

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2725394A (en) * 1950-08-03 1955-11-29 Ici Ltd Production of esters of orthophosphoric acid and salts thereof
US2866807A (en) * 1954-04-15 1958-12-30 Virginia Carolina Chem Corp Aliphatic aryl phosphites
US2929833A (en) * 1958-04-23 1960-03-22 Ethyl Corp Process of preparing phenyl dimethyl phosphates
US2960527A (en) * 1958-08-20 1960-11-15 Akad Wissenschaften Ddr Process for the preparation of dichloro phosphoric esters
US3059016A (en) * 1959-08-05 1962-10-16 Celanese Corp Manufacture of aryl phosphate esters
US3254142A (en) * 1961-09-01 1966-05-31 Bayer Ag Phosphorous acid esters

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002369A1 (de) 1979-01-24 1980-08-07 Minnesota Mining & Mfg Verfahren zur schmutz- und fleckenabweisenden ausruestung von textilen bodenbelaegen oder des textilen ausgangsmaterials und fluessiges mittel zur durchfuehrung des verfahrens
DE3051167C3 (de) * 1979-01-24 1994-11-24 Minnesota Mining & Mfg Fluorierte Alkohole
US4382891A (en) * 1980-05-09 1983-05-10 E. I. Du Pont De Nemours And Company Use of fluoroalkoxysulfur fluorides in fluorinations
US4517376A (en) * 1981-06-26 1985-05-14 E. I. Du Pont De Nemours And Company Manufacture of chloromethyl-substituted polyfluoroalkyl esters
US5242487A (en) * 1988-11-11 1993-09-07 Daikin Industries Ltd. Water- and oil-repellant composition
US20080113085A1 (en) * 2006-11-13 2008-05-15 Sheng Peng Polyfluoroether-based phosphates
US20080113200A1 (en) * 2006-11-13 2008-05-15 Sheng Peng Fluoroalkyl phosphate compositions
US7470818B2 (en) 2006-11-13 2008-12-30 E.I. Du Pont De Nemours & Company Fluoroalkyl phosphate compositions
US20090087670A1 (en) * 2006-11-13 2009-04-02 E. I. Du Pont De Nemours And Company Fluoroalkyl phosphate compositions
US7674928B2 (en) 2006-11-13 2010-03-09 E.I. Du Pont De Nemours And Company Polyfluoroether-based phosphates
US20100129668A1 (en) * 2006-11-13 2010-05-27 E.I. Du Pont De Nemours And Company Polyfluoroether-based phosphates
US7815816B2 (en) 2006-11-13 2010-10-19 E.I. Du Pont De Nemours And Company Polyfluoroether-based phosphates
US7951975B2 (en) 2006-11-13 2011-05-31 E.I. Du Pont De Nemours And Company Fluoroalkyl phosphate compositions
US8129568B2 (en) 2006-11-13 2012-03-06 E.I. Du Pont De Nemours And Company Fluoroalkyl phosphate compositions
CN110184847A (zh) * 2019-05-17 2019-08-30 华南理工大学 一种撕不烂仿皮纸及其制造方法与应用

Also Published As

Publication number Publication date
BE795705A (fr) 1973-08-21
GB1395454A (en) 1975-05-29
FR2173033B1 (en)) 1976-05-14
SU460615A3 (ru) 1975-02-15
DE2307204A1 (de) 1973-08-30
FR2173033A1 (en)) 1973-10-05
CH565724A5 (en)) 1975-08-29
JPS4896505A (en)) 1973-12-10

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